CN115518661A - Sulfur-tolerant shift catalyst, preparation method and application - Google Patents
Sulfur-tolerant shift catalyst, preparation method and application Download PDFInfo
- Publication number
- CN115518661A CN115518661A CN202110711565.0A CN202110711565A CN115518661A CN 115518661 A CN115518661 A CN 115518661A CN 202110711565 A CN202110711565 A CN 202110711565A CN 115518661 A CN115518661 A CN 115518661A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- catalyst
- solution
- shift catalyst
- tolerant shift
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 41
- 239000011593 sulfur Substances 0.000 claims abstract description 41
- 238000004073 vulcanization Methods 0.000 claims abstract description 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- QUEGLSKBMHQYJU-UHFFFAOYSA-N cobalt;oxomolybdenum Chemical compound [Mo].[Co]=O QUEGLSKBMHQYJU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 239000008367 deionised water Substances 0.000 claims description 43
- 229910021641 deionized water Inorganic materials 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 13
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 150000004763 sulfides Chemical class 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000001681 protective effect Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 241000219782 Sesbania Species 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 7
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical class [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000011066 ex-situ storage Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000008116 organic polysulfides Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a sulfur-tolerant shift catalyst, a preparation method and application thereof, belonging to the technical field of catalysts. The sulfur-tolerant shift catalyst is prepared from a carrier, an active component and an auxiliary agent, wherein alumina, magnesia and titanium oxide are used as the carrier; cobalt molybdenum oxide and sulfide are used as active components, and rare earth is used as an auxiliary agent. The sulfur-tolerant shift catalyst disclosed by the invention is low in vulcanization temperature, high in sulfur content and high in catalytic efficiency; the invention provides a preparation method and application of the sulfur-tolerant shift catalyst at the same time, which are simple and easy to implement, and adopt the pre-vulcanization process to form a protective film of elemental sulfur in the inner hole of the catalyst, so that the active component sulfide can be kept stable in the air, can stably exist in the air at normal temperature, is convenient to transport and store, does not need special vulcanization during industrial application, can obviously reduce the start-up time of the device, and have good economic benefit and application prospect.
Description
Technical Field
The invention relates to a sulfur-tolerant shift catalyst, a preparation method and application thereof, belonging to the technical field of catalysts.
Background
The cobalt-molybdenum series sulfur-resistant wide-temperature shift catalyst is mainly used in the chemical process of preparing raw material gas by using heavy raw materials such as heavy oil, residual oil, coal and the like, has lower activation temperature than Fe series high-temperature shift catalyst, is equivalent to Cu series low-temperature shift catalyst, has good heat resistance, has a wide active temperature region, and almost covers the whole active temperature region of Fe series high-temperature shift catalyst and Cu series low-temperature shift catalyst. In addition, the catalyst has the outstanding advantages of strong sulfur resistance and poison resistance, high strength, long service life and the like. The sulfuration is a process that the cobalt-molybdenum series sulfur-tolerant shift catalyst must go through, the process can change the cobalt-molybdenum active component in oxidation state into sulfuration state, so that the cobalt-molybdenum series sulfur-tolerant shift catalyst has shift activity, and the sulfuration process and the effect of the sulfur-tolerant shift catalyst directly affect the service performance of the catalyst.
The catalyst vulcanizing process is divided into a reactor internal on-line vulcanizing process and an external pre-vulcanizing process, and the external pre-vulcanizing technology has the advantages of improving the utilization rate of the vulcanizing agent, reducing the consumption of the vulcanizing agent, lightening the environmental pollution, reducing the start-up cost, shortening the start-up period and the like, so that the catalyst is increasingly applied in recent years. The ex-situ presulfurization technology can also be divided into two major classes, namely ex-situ presulfurization technology which is loaded by vulcanizing agents such as elemental sulfur, organic polysulfide, inorganic sulfide and hydrogen sulfide. The other is a technology that after the catalyst is normally vulcanized, the catalyst is passivated or pretreated, thereby improving the stability and initial activity of the vulcanized catalyst and facilitating the storage and transportation of the catalyst. The prevulcanization mode of loading the sulfur-containing compound is easy to lose along with gas in the temperature rise process of an industrial device due to various sulfides, so that the vulcanization degree is low, and the transformation activity and the service life of the industrial device are influenced.
Disclosure of Invention
The invention aims to provide a sulfur-tolerant shift catalyst which has low vulcanization temperature, high sulfur content and high catalytic efficiency; the invention also provides a preparation method and application of the sulfur-tolerant shift catalyst, which are simple and easy to implement, and adopt a pre-vulcanization process to form a protective film of elemental sulfur in an inner hole of the catalyst, so that active component sulfide can be kept stable in the air, can stably exist in the air at normal temperature, are convenient to transport and store, do not need special vulcanization during industrial application, can obviously reduce the start-up time of the device, and have good economic benefit and application prospect.
The sulfur-tolerant shift catalyst is prepared from a carrier, an active component and an auxiliary agent, wherein alumina, magnesia and titanium oxide are used as the carrier; cobalt molybdenum oxide and sulfide are used as active components, and rare earth is used as an auxiliary agent.
Preferably, the mass ratio of the cobalt metal content in the cobalt oxide to the molybdenum metal content in the molybdenum oxide is 1.5-4.
Preferably, the rare earth is a lanthanum containing oxide.
Preferably, the sulfur-tolerant shift catalyst comprises the following components in percentage by mass:
the metal content of Co is 1.0-5.0wt.%,
the content of Mo metal is 4-10 wt.%,
mg metal content 3.0-12.0wt.%,
al metal content 20.0-35.0wt.%,
ti metal content of 5.0-15.0wt.%,
the S content is 8.0-12.0wt.%,
the rare earth content is 0.1-0.5wt.%,
the balance being oxygen.
The preparation method of the sulfur-tolerant shift catalyst comprises the following steps:
(1) Dissolving citric acid in deionized water to form a solution A, then respectively dissolving cobalt nitrate, a rare earth additive and ammonium molybdate in the deionized water, sequentially pouring the solution A into the solution A, stirring the solution A while adding the solution at the temperature of 35-45 ℃, and keeping the temperature for a period of time; heating to 60-80 deg.C, stirring, aging until gel is formed, oven drying at 105-120 deg.C, and pulverizing to 200-250 mesh;
(2) Mixing the active metal powder with powdery aluminum-containing compound, magnesium-containing compound and titanium-containing compound, then adding a binder and an extrusion aid, uniformly mixing, extruding, forming, drying and roasting to obtain an oxidation state catalyst;
(3) Dissolving ammonium thiosulfate in water to obtain a solution B; equivalently dipping the oxidation state catalyst according to the water absorption rate of the oxidation state catalyst, and drying the oxidation state catalyst at the temperature of between 30 and 60 ℃;
(4) Dissolving sulfur in CS 2 In solution, as solution C; putting the dried catalyst into the solution C for second equivalent impregnation; this step uses a sulfur-containing CS 2 The solution is dipped and then is directly subjected to catalyst presulfurization without being dried;
(5) And (3) putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 120-140 ℃ in a nitrogen environment containing hydrogen, keeping the temperature for 2-4h, heating to 170-190 ℃, keeping the temperature for 3-5h, and cooling to normal temperature to obtain the pre-vulcanized catalyst containing part of active sulfides.
Preferably, in the step (1), the mass ratio of the citric acid to the total mass of the active components is 1.
Preferably, the aluminum-containing compound is pseudo-boehmite, alumina or alumina gel, and more preferably pseudo-boehmite.
Preferably, the magnesium compound is light magnesium oxide, magnesium carbonate or magnesium hydroxide, and more preferably light magnesium oxide.
Preferably, the titanium-containing compound is metatitanic acid or titanium oxide, and more preferably metatitanic acid.
Preferably, the binder is one or more of water, acetic acid, citric acid, oxalic acid or nitric acid, more preferably citric acid and/or oxalic acid, and the weight addition amount in the preparation process is 1-5%, preferably 2-4%. The adhesive has good compatibility with the main catalyst component, and ensures that the catalyst has higher strength and good stability.
Preferably, the extrusion aid is sesbania powder, citric acid, starch or sucrose, and is further preferably sesbania powder, and the weight addition amount in the preparation process is 1-8%, preferably 3-6%.
Preferably, the amount of ammonium thiosulfate used is 10-30wt% of the amount of the catalyst, and the amount of sulfur used is 8-18wt% of the amount of the catalyst.
Preferably, in the step (3), the drying temperature is 50 ℃.
Preferably, in the step (5), the hydrogen volume content is 20 to 60%, more preferably 40%, and the temperature increase rate is 30 to 40 ℃/h in the prevulcanization treatment.
The specific surface area of the presulfided catalyst prepared by the invention is 60m 2 /g～120m 2 The pore volume is not less than 0.30mL/g. The catalyst can be in the shape of strip, clover or sphere.
When the sulfur-tolerant shift catalyst is applied to sulfur-tolerant shift reaction, special vulcanization is not needed.
The invention takes alumina, magnesia and titanium oxide as main structures of carriers, takes cobalt molybdenum oxide and sulfide as active components, and the active components are added into carrier materials in a perovskite structure, the active components and auxiliary agents are uniformly dispersed and have moderate compatibility, and under the synergistic action of the active components and the carriers, the vulcanization temperature is greatly reduced, so that partial active component sulfide is more easily formed under the low-temperature condition; when the pre-sulfurization treatment is carried out, partial active component sulfide can be formed under the condition of low temperature, the catalyst has high sulfurization degree, and a protective film of elemental sulfur is formed in the inner hole of the catalyst, so that the active component sulfide can be kept stable in the air.
When the catalyst prepared by the invention is used on an industrial device, the sulfur protective film in the inner hole of the catalyst is stable and does not run off in the process of raising the temperature of nitrogen, when the process gas is started to conduct gas, the formed protective film can react with hydrogen in the process gas to generate hydrogen sulfide, the temperature of the inner hole is increased in a short time by changing reaction heat and the reaction heat generated by the hydrogen sulfide, the in-situ high-temperature deep vulcanization of active components of the catalyst is completed in the inner hole, and the vulcanization effect of the catalyst is enhanced. The catalyst has the advantages of simple and safe preparation method, high sulfur content, uniform dispersion of active sulfides, short catalyst pre-vulcanization time, stable existence in the air under the normal temperature condition, convenient transportation and storage, no need of special vulcanization during industrial application, remarkable reduction of the start-up time of the device, and good economic benefit and application prospect.
The invention has the following beneficial effects:
(1) The sulfur-resistant shift catalyst has low vulcanization temperature, high sulfur content and high catalytic efficiency;
(2) The preparation method of the sulfur-resistant shift catalyst is simple and easy to implement, and a prevulcanization process is adopted to form a protective film of elemental sulfur in an inner hole of the catalyst, so that the active component sulfide can be kept stable in the air and can stably exist in the air at normal temperature, and the sulfur-resistant shift catalyst is convenient to transport and store;
(3) When the sulfur-resistant shift catalyst is applied to the industry, special vulcanization is not needed, the start-up time of the device can be obviously reduced, and the sulfur-resistant shift catalyst has good economic benefit and application prospect.
Drawings
FIG. 1 is a schematic view of an apparatus for pressure evaluation of a catalyst prepared according to the present invention;
in the figure: 1. a raw material purifier; 2. a pressure reducer; 3. a mixer; 4. a pressure gauge; 5. a shutdown valve; 6. heating furnace; 7. a reaction tube; 8. a thermocouple tube inside the tube; 9. a condenser; 10. a separator; 11. a liquid discharge device; 12. a wet flow meter; 13. a vaporizer; 14. a water tank; 15. a water metering pump.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
Example 1
Dissolving 18g of citric acid in 60mL of deionized water to form a solution A, then respectively dissolving 12g of cobalt nitrate in 15mL of deionized water, dissolving 0.3g of lanthanum nitrate in 10mL of deionized water, dissolving 8.5g of ammonium heptamolybdate in 25mL of deionized water, slowly pouring into the solution A, stirring while adding at 40 ℃, keeping the temperature for 1h, then heating to 70 ℃, continuously stirring and aging for 2h until gel is formed, drying at 120 ℃, and crushing to 220 meshes. Mixing the active metal powder with 60g of pseudo-boehmite powder, 14g of light magnesium oxide powder and 15g of metatitanic acid powder, adding 6g of sesbania powder, uniformly mixing, dissolving 3g of citric acid and 2g of oxalic acid in 14mL of deionized water, adding the mixture into the powder, uniformly kneading, extruding, forming, drying and roasting to obtain the oxidation state catalyst.
Dissolving 28g of ammonium thiosulfate in 45mL of deionized water to obtain a solution B; 100g of oxidized cobalt molybdenum series is taken for sulfur-tolerant shift catalysis, equivalent impregnation is carried out according to the water absorption rate of 48%, and drying is carried out at 50 ℃.
12g of sulfur was dissolved in 40mL of CS 2 In solution, as solution C; and putting the dried catalyst into the solution B for secondary impregnation.
And (3) putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 120 ℃ at a heating rate of 30 ℃ in a nitrogen environment containing 40% of hydrogen, keeping the temperature for 2 hours, heating to 180 ℃, keeping the temperature for 3 hours, and cooling to normal temperature to obtain the pre-vulcanized catalyst S1 containing part of active sulfides.
Example 2
Dissolving 13g of citric acid in 55mL of deionized water to form a solution A, then respectively dissolving 25g of cobalt nitrate in 15mL of deionized water, dissolving 0.6g of lanthanum nitrate in 10mL of deionized water, dissolving 13.8g of ammonium heptamolybdate in 30mL of deionized water, slowly pouring into the solution A, stirring while adding at 35 ℃, keeping the temperature for 1h, then heating to 80 ℃, continuously stirring and aging for 2h until gel is formed, drying at 110 ℃, and crushing to 220 meshes. Mixing the active metal powder with 81g of pseudo-boehmite powder, 14.0g of magnesium carbonate powder and 21g of metatitanic acid powder, adding 6g of starch, uniformly mixing, then dissolving 2g of citric acid and 3g of oxalic acid in 15mL of deionized water, adding into the above powder, uniformly kneading, extruding, molding, drying and roasting to obtain the oxidation state catalyst.
Dissolving 12g of ammonium thiosulfate in 45mL of deionized water to obtain a solution B; 100g of an oxidized cobalt molybdenum sulfur-resistant shift catalyst was equivalently impregnated at a water absorption of 47%, and dried at 30 ℃.
15g of sulfur was dissolved in 40mL of CS 2 In solution, as solution C; and putting the dried catalyst into the solution B for secondary impregnation.
And (3) putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 100 ℃ at a heating rate of 40 ℃ in a nitrogen environment containing 60% of hydrogen, keeping the temperature for 2 hours, heating to 190 ℃, keeping the temperature for 3 hours, and cooling to normal temperature to obtain a pre-vulcanized catalyst S2 containing part of active sulfides.
Example 3
Dissolving 18g of citric acid in 45mL of deionized water to form a solution A, then respectively dissolving 4.9g of cobalt nitrate in 12mL of deionized water, dissolving 1.5g of lanthanum nitrate in 15mL of deionized water, and dissolving 7.5g of ammonium heptamolybdate in 20mL of deionized water, slowly pouring into the solution A, stirring while adding at 35 ℃, keeping the temperature for 1h, then heating to 60 ℃, continuously stirring and aging for 2h until gel is formed, drying at 105 ℃, and crushing to 220 meshes. Mixing the active metal powder with 47g of active alumina powder, 17g of light magnesium oxide powder and 22g of titanium oxide powder, adding 8g of sesbania powder and 1g of cane sugar, uniformly mixing, dissolving 1g of citric acid in 5mL of deionized water, adding the mixture into the powder, adding 5mL of dilute nitric acid, uniformly kneading, extruding, forming, drying and roasting to obtain the oxidation state catalyst.
Dissolving 18g of ammonium thiosulfate in 45mL of deionized water to obtain a solution B; 100g of an oxidized cobalt molybdenum sulfur-tolerant shift catalyst was equivalently impregnated at a water absorption of 45%, and dried at 30 ℃.
10g of sulfur was dissolved in 40mL of CS 2 In solution, as solution C; and putting the dried catalyst into the solution B for secondary impregnation.
And (3) putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 140 ℃ at a heating rate of 35 ℃ in a nitrogen environment containing 30% of hydrogen, keeping the temperature for 2 hours, heating to 160 ℃, keeping the temperature for 3 hours, and cooling to normal temperature to obtain a pre-vulcanized catalyst S3 containing part of active sulfides.
Example 4
Dissolving 20g of citric acid in 60mL of deionized water to form a solution A, then respectively dissolving 12g of cobalt nitrate in 15mL of deionized water, dissolving 0.3g of lanthanum nitrate in 10mL of deionized water, dissolving 8.5g of ammonium heptamolybdate in 25mL of deionized water, slowly pouring into the solution A, stirring while adding at 45 ℃, keeping the temperature for 1h, then heating to 75 ℃, continuously stirring and aging for 2h until gel is formed, drying at 120 ℃, and crushing to 220 meshes. Mixing the active metal powder with 84g of alumina gel powder, 14g of magnesium hydroxide powder and 15g of metatitanic acid powder, adding 6g of sesbania powder and 1g of starch, uniformly mixing, dissolving 3g of citric acid and 2mL of acetic acid in 10mL of deionized water, adding into the above powder, uniformly kneading, extruding, molding, drying and roasting to obtain the oxidation state catalyst.
8g of ammonium thiosulfate is dissolved in 45mL of deionized water to be used as a solution B; 100g of an oxidized cobalt molybdenum sulfur-tolerant shift catalyst was equivalently impregnated at a water absorption of 45%, and dried at 30 ℃.
18g of sulfur was dissolved in 40mL of CS 2 In solution, as solution C; and putting the dried catalyst into the solution B for secondary impregnation.
And (3) putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 140 ℃ at a heating rate of 35 ℃ in a nitrogen environment containing 30% of hydrogen, keeping the temperature for 2 hours, heating to 160 ℃, keeping the temperature for 3 hours, and cooling to normal temperature to obtain a pre-vulcanized catalyst S4 containing part of active sulfides.
Comparative example 1
28g of ammonium thiosulfate is dissolved in 45mL of deionized water to be used as a solution B; 100g of sulfur-tolerant cobalt-molybdenum shift catalyst QCS-03 (Cochler's chemical Co., ltd.) was immersed in an equivalent amount of 45% water absorption, and dried at 50 ℃.
12g of sulfur was dissolved in 40mL of CS 2 In solution, as solution C; and putting the dried catalyst into the solution B for secondary impregnation.
And (3) putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 120 ℃ at a heating rate of 30 ℃ in a nitrogen environment containing 40% of hydrogen, keeping the temperature for 2 hours, heating to 180 ℃, keeping the temperature for 3 hours, and cooling to normal temperature to obtain a pre-vulcanized catalyst D1 containing partial active sulfides.
Comparative example 2
Dissolving 12g of cobalt nitrate, 0.3g of lanthanum nitrate and 8.5g of ammonium heptamolybdate in 50mL of concentrated ammonia water to form a solution A, uniformly mixing 60g of pseudo-boehmite powder, 14g of light magnesium oxide powder, 15g of metatitanic acid powder and 6g of sesbania powder, adding the solution A, uniformly kneading, dissolving 3g of citric acid and 2g of oxalic acid in 10mL of deionized water, adding the mixture into the above materials, continuously kneading uniformly, extruding, forming, drying and roasting to obtain the oxidation-state catalyst.
28g of ammonium thiosulfate is dissolved in 45mL of deionized water to be used as a solution B; 100g of an oxidation state cobalt molybdenum sulfur-tolerant shift catalyst is taken, equally impregnated according to the water absorption rate of 45 percent, and dried at 50 ℃.
12g of sulfur was dissolved in 40mL of CS 2 In solution, as solution C; and putting the dried catalyst into the solution B for secondary impregnation.
And (3) putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 120 ℃ at a heating rate of 30 ℃ in a nitrogen environment containing 40% of hydrogen, keeping the temperature for 2 hours, heating to 180 ℃, keeping the temperature for 3 hours, and cooling to normal temperature to obtain a pre-vulcanized catalyst D2 containing part of active sulfides.
Comparative example 3
Dissolving 30g of citric acid in 80mL of deionized water to form a solution A, then respectively dissolving 12g of cobalt nitrate in 15mL of deionized water, dissolving 0.3g of lanthanum nitrate in 10mL of deionized water, dissolving 8.5g of ammonium heptamolybdate in 25mL of deionized water, slowly pouring into the solution A, stirring while adding at 40 ℃, keeping the temperature for 1h, then heating to 70 ℃, continuously stirring and aging for 2h until gel is formed, drying at 120 ℃, and crushing to 220 meshes. Mixing the active metal powder with 60g of pseudo-boehmite powder, 14g of light magnesium oxide powder and 15g of metatitanic acid powder, adding 6g of sesbania powder, uniformly mixing, dissolving 3g of citric acid and 2g of oxalic acid in 14mL of deionized water, adding the mixture into the powder, uniformly kneading, extruding, forming, drying and roasting to obtain the oxidation state catalyst.
28g of ammonium thiosulfate is dissolved in 45mL of deionized water to be used as a solution B; 100g of oxidation state cobalt molybdenum series sulfur-resistant transformation catalyst is taken, equivalent impregnation is carried out according to the water absorption rate of 45%, and drying is carried out at 60 ℃.
12g of sulfur was dissolved in 40mL of CS 2 In solution, as solution C; and putting the dried catalyst into the solution B for secondary impregnation.
And (3) putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 120 ℃ at a heating rate of 30 ℃ in a nitrogen environment containing 40% of hydrogen, keeping the temperature for 2 hours, heating to 180 ℃, keeping the temperature for 3 hours, and cooling to normal temperature to obtain a pre-vulcanized catalyst D3 containing part of active sulfides.
Comparative example 4
Dissolving 20g of citric acid in 60mL of deionized water to form a solution A, then respectively dissolving 12g of cobalt nitrate in 15mL of deionized water, dissolving 0.3g of lanthanum nitrate in 10mL of deionized water, dissolving 8.5g of ammonium heptamolybdate in 25mL of deionized water, slowly pouring into the solution A, stirring while adding at 40 ℃, keeping the temperature for 1h, then heating to 70 ℃, continuously stirring and aging for 2h until gel is formed, drying at 120 ℃, and crushing to 220 meshes. Mixing the active metal powder with 60g of pseudo-boehmite powder and 14g of light magnesium oxide powder, adding 6g of sesbania powder, uniformly mixing, dissolving 3g of citric acid and 2g of oxalic acid in 14mL of deionized water, adding the mixture into the powder, uniformly kneading, extruding, forming, drying and roasting to obtain the oxidation state catalyst.
28g of ammonium thiosulfate is dissolved in 45mL of deionized water to be used as a solution B; 100g of oxidation state cobalt molybdenum series sulfur-resistant transformation catalyst is taken, equivalent impregnation is carried out according to the water absorption rate of 45%, and drying is carried out at 60 ℃.
12g of sulfur was dissolved in 40mL of CS 2 In solution, as solution C; and putting the dried catalyst into the solution B for secondary impregnation.
And (3) putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 120 ℃ at a heating rate of 30 ℃ in a nitrogen environment containing 40% of hydrogen, keeping the temperature for 2 hours, heating to 180 ℃, keeping the temperature for 3 hours, and cooling to normal temperature to obtain a pre-vulcanized catalyst D4 containing part of active sulfides.
The results of the physicochemical properties and CO conversion at 300 ℃ of the catalysts in the examples of the present invention and the comparative examples, which were measured by a pressure evaluation apparatus, are shown in Table 1.
Wherein the raw material gas comprises the following components:
content of CO: 50.0 percent;
CO 2 the contents are as follows: 3.0 percent;
H 2 and (2) S content: more than 0.2 percent;
and the balance: h 2 。
Catalyst loading: 50mL;
and (3) heating process: and starting to switch process gas and feeding water for testing when the temperature is raised to 220 ℃ by adopting nitrogen.
Catalyst pressurization evaluation conditions:
inlet temperature: 300 ℃; pressure: 4.0MPa; water/gas: 1.2;
dry gas space velocity: 3000h -1 ；H 2 And (2) S content: 0.2% -0.3%; time: and (4) 40h.
TABLE 1 catalyst pressure Activity and Sulfur content
| Examples | Catalyst numbering | CO conversion at 300% | Sulfur content in the catalyst% |
| 1 | S1 | 93.5 | 11.2 |
| 2 | S2 | 93.3 | 12.0 |
| 3 | S3 | 93.2 | 10.8 |
| 4 | S4 | 93.4 | 11.6 |
| 5 | D1 | 93.0 | 10.2 |
| 6 | D2 | 92.9 | 9.4 |
| 7 | D3 | 92.2 | 11.2 |
| 8 | D4 | 91.4 | 11.0 |
As can be seen from the evaluation results in Table 1, the comprehensive physical and chemical properties of the catalyst, the CO conversion rate at 300 ℃ and the sulfur content are obviously better than those of the comparative example.
Claims (10)
1. A sulfur tolerant shift catalyst is prepared from a carrier, an active component and an auxiliary agent, and is characterized in that: taking alumina, magnesia and titania as carriers; cobalt molybdenum oxide and sulfide are used as active components, and rare earth is used as an auxiliary agent.
2. The sulfur-tolerant shift catalyst according to claim 1, characterized in that: the mass ratio of the cobalt metal content in the cobalt oxide to the molybdenum metal content in the molybdenum oxide is 1.5-4.
3. The sulfur tolerant shift catalyst of claim 1, wherein: the rare earth is lanthanum-containing oxide.
4. The sulfur tolerant shift catalyst of claim 1, wherein: the paint comprises the following components in percentage by mass:
the metal content of Co is 1.0-5.0wt.%,
the content of Mo metal is 4-10 wt.%,
mg metal content 3.0-12.0wt.%,
al metal content 20.0-35.0wt.%,
ti metal content of 5.0-15.0wt.%,
the S content is 8.0-12.0wt.%,
the rare earth content is 0.1-0.5wt.%,
the balance being oxygen.
5. A process for preparing a sulfur tolerant shift catalyst as claimed in any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) Dissolving citric acid in deionized water to form a solution A, then respectively dissolving cobalt nitrate, a rare earth additive and ammonium molybdate in the deionized water, sequentially pouring the solution A into the solution A, stirring the solution A while adding the solution at the temperature of 35-45 ℃, and keeping the temperature for a period of time; heating to 60-80 deg.C, stirring, aging until gel is formed, oven drying at 105-120 deg.C, and pulverizing to 200-250 mesh;
(2) Mixing the active metal powder with powdery aluminum-containing compound, magnesium-containing compound and titanium-containing compound, then adding a binder and an extrusion aid, uniformly mixing, extruding, forming, drying and roasting to obtain an oxidation state catalyst;
(3) Dissolving ammonium thiosulfate in water to obtain a solution B; equivalently dipping the oxidation state catalyst according to the water absorption rate of the oxidation state catalyst, and drying the oxidation state catalyst at the temperature of between 30 and 60 ℃;
(4) Dissolving sulfur in CS 2 In solution, as solution C; putting the dried catalyst into the solution C for second equivalent impregnation;
(5) And putting the impregnated catalyst into a pre-vulcanization treatment device, heating to 120-140 ℃ in a nitrogen environment containing hydrogen, keeping the temperature for 2-4h, heating to 170-190 ℃, keeping the temperature for 3-5h, and cooling to normal temperature to obtain the sulfur-resistant shift catalyst containing part of active sulfides.
6. The method of preparing a sulfur tolerant shift catalyst according to claim 5, wherein: in the step (1), the mass ratio of the citric acid to the total mass of the active components is 1.
7. The method of preparing a sulfur tolerant shift catalyst according to claim 5, wherein: the aluminum-containing compound is pseudo-boehmite, alumina or alumina gel; the magnesium-containing compound is light magnesium oxide, magnesium carbonate or magnesium hydroxide; the titanium-containing compound is metatitanic acid or titanium oxide; the binder is one or more of water, acetic acid, citric acid, oxalic acid or nitric acid; the extrusion aid is sesbania powder, citric acid, starch or sucrose.
8. The method of preparing a sulfur tolerant shift catalyst according to claim 5, wherein: the dosage of the ammonium thiosulfate is 10-30wt% of the dosage of the catalyst, and the dosage of the sulfur is 8-18wt% of the dosage of the catalyst.
9. The method of preparing a sulfur tolerant shift catalyst according to claim 5, wherein: in the step (5), during the pre-vulcanization treatment, the volume content of the hydrogen is 20-60%, and the heating rate is 30-40 ℃/h.
10. Use of a sulfur tolerant shift catalyst as claimed in any one of claims 1 to 4, wherein: the sulfur-tolerant shift catalyst is directly applied to sulfur-tolerant shift reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110711565.0A CN115518661B (en) | 2021-06-25 | 2021-06-25 | Sulfur-tolerant shift catalyst, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110711565.0A CN115518661B (en) | 2021-06-25 | 2021-06-25 | Sulfur-tolerant shift catalyst, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115518661A true CN115518661A (en) | 2022-12-27 |
| CN115518661B CN115518661B (en) | 2023-12-05 |
Family
ID=84694900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110711565.0A Active CN115518661B (en) | 2021-06-25 | 2021-06-25 | Sulfur-tolerant shift catalyst, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115518661B (en) |
Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241452A (en) * | 1998-07-15 | 2000-01-19 | 中国石化齐鲁石油化工公司 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
| JP2004330110A (en) * | 2003-05-08 | 2004-11-25 | Chiyoda Corp | Method for manufacturing denitrification catalyst |
| CN1557556A (en) * | 2004-02-13 | 2004-12-29 | 中国石油天然气集团公司 | In situ outer prevulcanization method for hydrogenation catalyst |
| CN1994567A (en) * | 2006-12-20 | 2007-07-11 | 中国科学院山西煤炭化学研究所 | Hydrogenation catalyst precuring method |
| RU2311959C1 (en) * | 2006-10-13 | 2007-12-10 | Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук | Catalyst, carrier preparation method, catalyst preparation method, and diesel fraction hydrodesulfurization process |
| US20110124494A1 (en) * | 2009-11-24 | 2011-05-26 | Oleg Mironov | Hydroprocessing Bulk Catalyst and Methods of Making Thereof |
| KR20110075323A (en) * | 2009-12-28 | 2011-07-06 | 주식회사 포스코 | Method of water gas shift reaction and method for producing hydrogen using the same |
| CN103447057A (en) * | 2012-05-31 | 2013-12-18 | 武汉科林精细化工有限公司 | Preparation method of pre-vulcanized selective hydrodesulfurization catalyst for FCC gasoline |
| CN104248961A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN105233867A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Presulfided sulfur-tolerant shift catalyst and preparation method |
| CN106179524A (en) * | 2016-07-08 | 2016-12-07 | 昌邑凯特新材料有限公司 | A kind of method for pre-sulphuration of CO sulfur-resistant transformation catalyst |
| CN106552637A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Cobalt molybdenum system low temperature sulfur tolerant shift catalyst and preparation method |
| CN106669855A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Method for preparing vulcanization type hydrogenation catalyst molded at one step |
| WO2018044241A1 (en) * | 2016-09-05 | 2018-03-08 | Agency For Science, Technology And Research | Method of producing a methanation catalyst |
| CN108786837A (en) * | 2017-04-26 | 2018-11-13 | 神华集团有限责任公司 | Sulfur-resistant transformation catalyst and preparation method thereof |
| CN109621968A (en) * | 2017-10-09 | 2019-04-16 | 中国石油化工股份有限公司 | The high pressure transformation catalyst of resistance to low-sulfur and preparation method |
| US20190232269A1 (en) * | 2016-09-12 | 2019-08-01 | China Petroleum & Chemical Corporation | Hydrogenation catalyst, its production and application thereof |
| CN110876940A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN111659409A (en) * | 2020-06-04 | 2020-09-15 | 深圳市汇德丰控股集团有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
| CN111744494A (en) * | 2020-06-11 | 2020-10-09 | 北京华电光大环境股份有限公司 | Flat plate type CO and SO2And NOxSynchronous removal catalyst and preparation method thereof |
| CN114100625A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Cobalt-molybdenum-based perovskite type sulfur-tolerant shift reaction catalyst and preparation method thereof |
| WO2022089072A1 (en) * | 2020-10-27 | 2022-05-05 | 中国石油化工股份有限公司 | Catalyst and method for sulfur-tolerant shift catalytic reaction |
-
2021
- 2021-06-25 CN CN202110711565.0A patent/CN115518661B/en active Active
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241452A (en) * | 1998-07-15 | 2000-01-19 | 中国石化齐鲁石油化工公司 | Hydration-resisting and sulfur-resisting conversion catalyst and its preparation |
| JP2004330110A (en) * | 2003-05-08 | 2004-11-25 | Chiyoda Corp | Method for manufacturing denitrification catalyst |
| CN1557556A (en) * | 2004-02-13 | 2004-12-29 | 中国石油天然气集团公司 | In situ outer prevulcanization method for hydrogenation catalyst |
| RU2311959C1 (en) * | 2006-10-13 | 2007-12-10 | Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук | Catalyst, carrier preparation method, catalyst preparation method, and diesel fraction hydrodesulfurization process |
| CN1994567A (en) * | 2006-12-20 | 2007-07-11 | 中国科学院山西煤炭化学研究所 | Hydrogenation catalyst precuring method |
| US20110124494A1 (en) * | 2009-11-24 | 2011-05-26 | Oleg Mironov | Hydroprocessing Bulk Catalyst and Methods of Making Thereof |
| KR20110075323A (en) * | 2009-12-28 | 2011-07-06 | 주식회사 포스코 | Method of water gas shift reaction and method for producing hydrogen using the same |
| CN103447057A (en) * | 2012-05-31 | 2013-12-18 | 武汉科林精细化工有限公司 | Preparation method of pre-vulcanized selective hydrodesulfurization catalyst for FCC gasoline |
| CN104248961A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN105233867A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Presulfided sulfur-tolerant shift catalyst and preparation method |
| CN106552637A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Cobalt molybdenum system low temperature sulfur tolerant shift catalyst and preparation method |
| CN106669855A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Method for preparing vulcanization type hydrogenation catalyst molded at one step |
| CN106179524A (en) * | 2016-07-08 | 2016-12-07 | 昌邑凯特新材料有限公司 | A kind of method for pre-sulphuration of CO sulfur-resistant transformation catalyst |
| WO2018044241A1 (en) * | 2016-09-05 | 2018-03-08 | Agency For Science, Technology And Research | Method of producing a methanation catalyst |
| US20190232269A1 (en) * | 2016-09-12 | 2019-08-01 | China Petroleum & Chemical Corporation | Hydrogenation catalyst, its production and application thereof |
| CN108786837A (en) * | 2017-04-26 | 2018-11-13 | 神华集团有限责任公司 | Sulfur-resistant transformation catalyst and preparation method thereof |
| CN109621968A (en) * | 2017-10-09 | 2019-04-16 | 中国石油化工股份有限公司 | The high pressure transformation catalyst of resistance to low-sulfur and preparation method |
| CN110876940A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN111659409A (en) * | 2020-06-04 | 2020-09-15 | 深圳市汇德丰控股集团有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
| CN111744494A (en) * | 2020-06-11 | 2020-10-09 | 北京华电光大环境股份有限公司 | Flat plate type CO and SO2And NOxSynchronous removal catalyst and preparation method thereof |
| CN114100625A (en) * | 2020-08-31 | 2022-03-01 | 中国石油化工股份有限公司 | Cobalt-molybdenum-based perovskite type sulfur-tolerant shift reaction catalyst and preparation method thereof |
| WO2022089072A1 (en) * | 2020-10-27 | 2022-05-05 | 中国石油化工股份有限公司 | Catalyst and method for sulfur-tolerant shift catalytic reaction |
Non-Patent Citations (3)
| Title |
|---|
| JINGFANG SUN等: "Comparative study on the catalytic CO oxidation properties of CuO/CeO2 catalysts prepared by solid state and wet impregnation", 《CHINESE JOURNAL OF CATALYSIS》, pages 1347 - 1358 * |
| 刘志杰等: "加氢催化剂预硫化剂的应用现状及展望", 《石化技术与应用》, pages 74 - 79 * |
| 张孔远等: "CoMo型耐硫变换催化剂不同硫化剂的器外预硫化研究", 《燃料化学学报》, pages 346 - 354 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115518661B (en) | 2023-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102348503B (en) | For oil and the polar additive dip composition of hydrocarbon catalytic hydrogenation treatment, prepare the method for this catalyst, and use the method for this catalyst | |
| CN104646010A (en) | Process improvement method of vulcanized hydrogenation refining catalyst | |
| CN106513006B (en) | A kind of preparation method of body phase Hydrobon catalyst | |
| CN106512984B (en) | A kind of preparation method of high activity diesel hydrogenation for removal sulphur catalyst | |
| CN101439289A (en) | Preparation of hydrogenation catalyst | |
| CN102284299B (en) | Vulcanization method for hydrogenation catalyst and application thereof | |
| CN107469836B (en) | Sulfur tail gas hydrogenation catalyst and preparation method thereof | |
| CN102896001B (en) | Preparation method for cascade porous ZIFs and hydrogen desulfurization catalyst | |
| CN107446616A (en) | One kind is hydrocracked start-up method | |
| CN1283361C (en) | In situ outer prevulcanization method for hydrogenation catalyst | |
| CN104841493A (en) | On-site external vulcanization processing method of hydrogenation catalysts | |
| CN101590437B (en) | Ex-situ presulfurizing method of hydrogenation catalyst | |
| CN1237150C (en) | Sulfurated hydrogenation catalyst and its preparing process | |
| CN106552649A (en) | Presulfurization sulfur-resistant transformation catalyst and preparation method thereof | |
| CN109772387B (en) | Hydrotreating catalyst and preparation method thereof | |
| CN103100395B (en) | The preparation method of sulfide type catalyst | |
| CN115518661A (en) | Sulfur-tolerant shift catalyst, preparation method and application | |
| CN101618330B (en) | Method for preparing vulcanization catalyst | |
| CN101590416A (en) | Molybdenum-nickel hydrogenation catalyst and preparation method thereof | |
| CN1766047A (en) | Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method | |
| CN114433092B (en) | Pre-sulfiding method of hydrogenation catalyst, obtained pre-sulfiding hydrogenation catalyst and application | |
| CN108355691A (en) | A kind of preparation method of oxidation-desulfurizing catalyst | |
| CN111298800A (en) | Hydrodesulfurization catalyst and preparation method and application thereof | |
| CN112742404A (en) | Gasoline selective hydrodesulfurization catalyst, preparation method and application thereof, and gasoline selective hydrodesulfurization method | |
| CN115999585B (en) | Supported sulfidation hydrogenation catalyst with atomic dispersion Mo as auxiliary agent, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |